Synthesis of Au@Ag core-shell nanocubes with finely tuned shell thicknesses for surface-enhanced Raman spectroscopic detection.

In this work, we describe a facile method for generating monodisperse Au@Ag core-shell nanocubes with well-controlled size and fine-tuned Ag shell thicknesses. In this synthesis method, Au nanocubes were prepared via the seed-mediated growth method. Then, Au@Ag nanocubes with the core-shell structure were prepared separately by reducing AgNO3 with AA using as-prepared Au nanocubes as seeds. The thickness of Ag shells could be finely tuned from 3.6 nm to 10.0 nm by varying the concentration of the AgNO3 precursor. By investigating the localized surface plasmon resonance (LSPR) properties of Au@Ag nanocubes in relation to the thickness of the Ag shell, we found that the intensity of the characteristic peak of Ag gradually increases and that of Au gradually decreases as the thickness of the Ag shell increases. Additionally, surface-enhanced Raman scattering (SERS) properties of Au@Ag core-shell nanocubes were evaluated using rhodamine 6G (R6G) as the probe molecule. Interestingly, Au@Ag nanocubes exhibit efficient SERS intensities compared to the Au nanocubes, and Ag shell with a thickness of about 8.4 nm exhibits the optimal SERS activity. In addition, our results also demonstrated that Au@Ag nanocubes with an Ag shell thickness of 8.4 nm exhibited high SERS sensitivity and are capable of probing the analyte down to 10-12 M. The results obtained here suggest that Au@Ag core-shell nanocubes might serve as a nanoprobe for SERS-based analytical and biosensing applications.

Shape controlled synthesis of concave octahedral Au@AuAg nanoparticles to improve their surface-enhanced Raman scattering performance.

In this work, a seed mediated strategy has been proposed to design and fabricate uniform octahedral shaped gold@gold-silver nanoparticles (Au@AuAg NPs) with unique concave structure and an AuAg alloy shell. The morphology and Au/Ag ratio of the Au@AuAg nanostructures can be delicately controlled by varying the concentration of reagents, namely the Au nanorod (NR) seeds, HAuCl4 and AgNO3 precursor. Besides, the investigation of the growth mechanism revealed that the morphology of the product also can be controlled by tuning the growth time. Furthermore, uniformly arranged assemblies of concave octahedral Au@AuAg NPs were prepared through a solvent evaporation self-assembly strategy and employed as surface-enhanced Raman scattering (SERS) substrates, effectively applied to the analysis of R6G for the examination of SERS performance. Satisfyingly, owing to the synergistic effect between the Au and Ag elements and concave structure, concave octahedral Au@AuAg NPs exhibit significantly higher SERS enhancement compared with traditional octahedral Au NPs, which have an enhancement factor of ∼1.3 × 107 and a detection limit as low as 10-10 M. Meanwhile, the SERS substrate reveals an excellent uniformity and reproducibility of the SERS performance. This work opens a new avenue toward bimetallic NPs with concave structure, which have broad application prospects in optics, SERS detection and other fields.

Fabrication of a three-dimensional (3D) SERS fiber probe and application of in situ detection.

Surface-enhanced Raman scattering (SERS) fiber probes are useful for remote and online detection of harmful molecules using the SERS effect. In this study, a 3-dimensional (3D) SERS optical fiber probe is proposed. The formation of the 3D optical fiber probe mainly included three steps: construction of monolayer polystyrene (PS) spheres as a mask on the end face of the fiber, reactive ion etching (RIE) for PS spheres and fibers, and metal sputtering deposition. Compared with flat surface fiber probes, these 3D SERS fiber probes are composed of ordered nanocolumn arrays, which have the advantages of a simple manufacturing process, low cost, high sensitivity, and good stability. The structures of the 3D SERS fiber probe can be well controlled by changing the size of the PS sphere and etching time. The formation of the nanocolumn was studied using time evolution experiments. The obtained fiber SERS probe has good stability and high sensitivity for the in situ detection of 4-aminothiophenol (4-ATP) in solution. Therefore, these 3D SERS fiber probes have potential applications in harmful molecules for real-time detection.

Synthesis of Uniform Gold Nanorods with Large Width to Realize Ultralow SERS Detection.

In this work, we successfully demonstrate high-yield synthesis of high-quality gold nanorods (Au NRs) with width ranging from 6.5 nm to 175 nm by introducing heptanol molecules as secondary templating agents during cetyltrimethylammonium bromide-templated, seeded growth method. The results show that an appropriate concentration of heptanol molecules not only alter the micellization behavior of CTAB in water, but also help silver ions impact the symmetry-breaking efficiency of additional Au-NP seeds in addition to enhancing the utilization of gold precursors. Moreover, the generality and versatility of the present strategy for synthesis of Au NRs with flexible controlled dimensions are further demonstrated by successful synthesis of Au NRs with the assistance of other fatty alcohols with properly long alkyl chains. Furthermore, when arrays of vertically aligned Au NRs with large width (AVA-Au120×90 NRs) are used as SERS substrates, they can achieve the ultralow limit of detection for crystal violet (10-16  M) with good reliability and reproducibility, and the rapid detection and identification of residual harmful substances.

Synthesis of large gold nanoparticles with deformation twinnings by one-step seeded growth with Cu(ii)-mediated Ostwald ripening for determining nitrile and isonitrile groups.

In this work, uniform and large gold nanoparticles (Au NPs) including quasi-spherical (QS) Au NPs with average diameters of 70 to 196 nm and trisoctahedral (TOH) Au NPs with average diameters of 140 to 195 nm were successfully synthesized by controlling the concentration of Cu2+ ions and the particle number of 3 nm Au-NP seeds, respectively, using a one-step seeded growth method with Cu2+-mediated Ostwald ripening. It is found that because of the concentration-dependent under-potential deposition of Cu2+ ions (CuUPD), 3 nm Au-NP seeds are firstly changed into Au NPs with a controlled QS- or TOH shape at the initial growth stage, followed by the conformal growth of Au atoms onto the initially formed Au NPs due to Cu2+-mediated Ostwald ripening, in which the extra Au atoms come from the dissolution of in situ Au nuclei by the unavoidable self-nucleation. Moreover, the as-prepared QS Au NPs with a rough surface exhibit a better SERS performance for physically adsorbed probes (crystal violet, CV) than the TOH Au NPs with sharp tips and with a comparable size. Furthermore, the as-prepared QS Au NPs can be used to distinguish nitrile and isonitrile groups by surface-enhanced Raman scattering (SERS) due to the presence of deformation twinnings. Thus, the as-prepared QS Au NPs with a rough surface and deformation twinnings can be further used as templates for the fabrication of bimetallic materials with multi-functionalities.

Compressive Strain in Core-Shell Au-Pd Nanoparticles Introduced by Lateral Confinement of Deformation Twinnings to Enhance the Oxidation Reduction Reaction Performance.

In this work, quasi-spherical, uniform gold nanoparticles with rich deformation twinning (Audt NPs) were first synthesized with the assistance of copper(II) ions. Then, these Audt NPs were used as the cores for the fabrication of core-shell (CS) Audt-Pd NPs with ultrathin Pd layers, which also can bear compressive strain because of the formation of corrugated structured Pd shells led by the lateral confinement imposed by deformation twinning in the Au cores. The presence of compressive strain in the CS Audt-Pd NPs can result in the widening of the d-band width of the Pd shell and further the downshift of their d-band center, which can then improve the desorption ability of intermediates and still maintain the adsorption ability of the reactants because of the broad adsorption potential range. Taking the oxidation reduction reaction and the ethanol oxidation reaction as examples, the as-prepared Audt-Pd NPs indeed exhibited superior catalytic performances because of the synergism of compressive strain and the electronic effect. Thus, our work opens a new way to introduce compressive strain in the Pd-based CS NP catalysts, which can achieve the enhancement in the electrocatalytic performance by combining the merit of compressive strain and the electronic effect.

pH-Dependent growth of atomic Pd layers on trisoctahedral gold nanoparticles to realize enhanced performance in electrocatalysis and chemical catalysis.

In this work, the controlled epitaxial growth of ultrathin Pd shells of a few atomic layers (denoted as nL) on the surfaces of gold nanoparticle (Au NP) cores of different morphologies (trisoctahedral, cubic, and spherical shapes) in the presence of cetyltrimethylammonium chloride (CTAC) was achieved by regulating the pH value of the aqueous CTAC solution and finely tuning the amount of the Pd precursor. It was found that the critical shell thickness for epitaxial Pd growth at the optimal pH value was 4 atomic layers, taking {331}-faceted trisoctahedral (TOH) Au@PdnL NPs as an example, on the basis of the results of atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images. Moreover, the resulting TOH Au@Pd1L NPs (100.9 m2 g-1, 13.2 A mgPd-1 and 13.1 mA cm-2) exhibited excellent electrocatalytic performance and long-term electrocatalytic activity for ethanol oxidation, around 4.8-fold, 66-fold, and 21.8-fold better than commercial Pd/C catalysts (31 m2 g-1, 0.2 A mgPd-1, and 0.6 mA cm-2). Furthermore, the resulting TOH Au@Pd1L NPs not only markedly enhance the chemical catalytic activity for the reduction of 4-nitrophenol (4-NP), but also allow the in situ surface-enhanced Raman spectroscopy (SERS) monitoring of the reaction process of the Pd-catalyzed reduction of 4-NTP. Thus, our work may provide a new way to fabricate core-shell (CS) bimetallic NPs with the merits of both metal outer shells (excellent catalytic performance in electrocatalysis and chemical catalysis) and Au NP cores (reaction process by in situ SERS monitoring).

Regulating Surface Facets of Metallic Aerogel Electrocatalysts by Size-Dependent Localized Ostwald Ripening.

It is well known that the activity and stability of electrocatalysts are largely dependent on their surface facets. In this work, we have successfully regulated surface facets of three-dimensional (3D) metallic Au m- n aerogels by salt-induced assembly of citrate-stabilized gold nanoparticles (Au NPs) of two different sizes and further size-dependent localized Ostwald ripening at controlled particle number ratios, where m and n represent the size of Au NPs. In addition, 3D Au m- n-Pd aerogels were further synthesized on the basis of Au m- n aerogels and also bear controlled surface facets because of the formation of ultrathin Pd layers on Au m- n aerogels. Taking the electrooxidation of small organic molecules (such as methanol and ethanol) by the resulting Au m- n and Au m- n-Pd aerogels as examples, it is found that surface facets of metallic aerogels with excellent performance can be regulated to realize preferential surface facets for methanol oxidation and ethanol oxidation, respectively. Moreover, they also indeed simultaneously bear high activity and excellent stability. Furthermore, their activities and stability are also highly dependent on the area ratio of active facets and inactive facets on their surfaces, respectively, and these ratios are varied via the mismatch of sizes of adjacent NPs. Thus, this work not only demonstrates the realization of the regulation of the surface facets of metallic aerogels by size-dependent localized Ostwald ripening but also will open up a new way to improve electrocatalytic performance of 3D metallic aerogels by surface regulation.

Understanding the effect of ultrathin AuPd alloy shells of irregularly shaped Au@AuPd nanoparticles with high-index facets on enhanced performance of ethanol oxidation.

In this study, irregularly shaped, concave cuboidal Au@AuPd nanoparticles (ISCC-Au@AuPd NPs) with high-index facets were synthesized via Pd overgrowth on pre-formed ISCC-Au NPs with a concentration of Pd precursors as low as 2%. The AuPd alloy nature of the resulting shells was confirmed by X-ray photoelectron spectroscopy, cyclic voltammogram analysis, and energy dispersive X-ray spectroscopy. Among the irregularly shaped NPs obtained, the ISCC-Au97.5@Au0.5Pd2.0 NPs display the largest electrochemically active surface area (up to 92.11 m(2) g(-1)), as their closed-packed agglomeration was prevented, and the best long-term stability with respect to ethanol oxidation (0.50 M) in alkaline media (0.30 KOH) by efficiently removing intermediates. Their mass- and ECSA-normalized current densities (4.15 A mgPd(-1) and 4.51 mA cm(-2)) are about 20.7 times and 6.9 times higher than those of commercial Pd/C catalysts (0.20 A mgPd(-1) and 0.65 mA cm(-2)), respectively.

{331}-Faceted trisoctahedral gold nanocrystals: synthesis, superior electrocatalytic performance and highly efficient SERS activity.

We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by using 3.0 nm CTAC-Au seeds or as-prepared 70 nm TOH Au NCs as seeds. We find that the electrocatalytic performance on methanol oxidation and surface enhancement Raman spectroscopy (SERS) activity of {331}-faceted TOH Au NCs is size-dependent. In comparison with well-known nanoporous gold (0.088 mA cm(-2)), {331}-faceted TOH Au NCs with sizes of 110 nm exhibit fairly high catalytic activity (0.178 mA cm(-2)) on methanol oxidation (1.0 M) in alkaline media due to the presence of increasing density of atomic steps, ledges, and kinks on the NC surfaces. Their current density is reduced by less than 7% after 500 cycling tests. {331}-Faceted TOH Au NCs with sizes of 175 nm exhibit the highest SERS activity for 4-aminothiophenol (4-ATP) molecules. The enhancement factors of a1 modes of 4-ATP molecules can reach the order of 10(9) when the 4-ATP concentration is 3 × 10(-6) M. Moreover, Raman signals (ag modes) of 4,4'-dimercaptoazobenzene (DMAB) molecules on TOH Au NCs are stronger than those on spherical Au NCs of comparable size due to the enhanced laser-induced transformation of 4-ATP molecules by high-index {331}-facets during SERS measurement. Furthermore, the SERS intensities of 4-methylbenzenethiol (4-MTP) molecules on TOH Au NCs are also higher than those on spherical Au NCs of comparable size due to sharp extremities.